US4104228A - Linear, partially deacylated poly(N-acyl)alkylenimines as tannin migration inhibitors - Google Patents

Linear, partially deacylated poly(N-acyl)alkylenimines as tannin migration inhibitors Download PDF

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US4104228A
US4104228A US05/754,398 US75439876A US4104228A US 4104228 A US4104228 A US 4104228A US 75439876 A US75439876 A US 75439876A US 4104228 A US4104228 A US 4104228A
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poly
acyl
alkylenimine
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tannin
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Victor E. Meyer
Kenneth M. Kem
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Dow Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
    • C09D5/024Emulsion paints including aerosols characterised by the additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines
    • C08G73/0233Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02Polyamines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • Y10T428/31989Of wood

Definitions

  • This invention relates to tannin-containing wood substrates.
  • this invention relates to a latex paint applied to the surface of said substrate.
  • this invention relates to a method of inhibiting tannin migration through the latex paint.
  • this invention relates to the use of a poly(N-acyl)alkylenimine as a tannin migration inhibitor.
  • Harren et al., U.S. Pat. No. 3,494,878, teach incorporating an ion exchange resin into an aqueous coating composition comprised of a dispersed emulsion polymer of vinyl addition type and applying the combination to cedar and redwood type substrates.
  • the ion exchange resin is highly cross-linked.
  • Nordyke et al. U.S. Pat. No. 3,852,087, teach a method of inhibiting the migration of water-soluble tannins through a paint film applied to a tannin-containing wood by incorporating doping agents into certain composite pigments.
  • Enumerated doping agents included the amphoteric compounds of alumina, titania, zirconium, silica or zinc.
  • Lalk et al. U.S. Pat. No. 3,900,619, teach inhibiting tannin migration through a latex paint applied to the surface of a tannin-containing wood substrate by applying to the substrate a water-soluble S-arylcycloaliphatic sulfonium compound. These sulfonium compounds can be applied to the wood substrate either prior to or concurrently with the application of the latex paint.
  • tannin migration through a latex paint applied to a tannin-containing wood surface is inhibited by the novel method comprising applying to the wood surface an inhibiting amount of a linear, partially deacylated poly(N-acyl)alkylenimine (PAAI) having a weight average molecular weight of at least about 10,000.
  • PAAI can be applied to the wood surface either prior to or concurrently with the latex paint.
  • high (above 50,000) molecular weight and high (above 20 percent) deacylated PAAI also has desirable thickening properties.
  • PAAI's are known compounds (I) and are readily prepared by the ring-opening polymerization of substituted oxazolines (II) followed by hydrolysis. ##STR1## The substituents are later defined.
  • the ring-opening polymerization is generally conducted in the presence of a cationic polymerization catalyst at a reaction temperature of about 0°-200° C.
  • Typical catalysts include strong mineral acids, organic sulfonic acids and their esters, acidic salts such as ammonium sulfate, Lewis acids such as aluminum trichloride, stannous tetrachloride, borontrifluoride, and organic diazoniumfluoroborates, dialkyl sulfates, and other like catalysts.
  • the pre-hydrolyzed polymers thereby obtained are linear N-acylated polyalkylenimines having a molecular structure consisting essentially of repeating units of the formula ##STR2## These polymers are easily deacylated by acid, base or neutral hydrolysis. Hydrolysis (deacylation) is best controlled under acidic conditions and acid hydrolysis is thus preferred.
  • the partially deacylated PAAI's have a molecular structure consisting essentially of repeating units of the formula ##STR3## wherein n (for both III and IV) is the total number of units, h is the number of deacylated units, and n-h is the number of acylated units.
  • R' is typically hydrogen or R, and R is typically an alkyl or an inertly-substituted alkyl radical of 1-3 carbon atoms.
  • the combined carbon content of R and R' generally does not exceed 4 alkyl carbon atoms.
  • R and R' alkyl or inertly substituted alkyl radicals of 4 or more carbon atoms or of a combined alkyl carbon content of 5 or more carbon atoms diminish generally the water solubility of the PAAI polymer, thus diminish generally the polymer's compatibility with latex patent systems, and are thus generally disfavored.
  • R and R' have sufficient hydrophilic, inert substituents, such as ether oxygen, carbonyl, ester, etc., to render the PAAI polymer sufficiently water-soluble to be compatible with a latex paint system, then R and R' can favorably be alkyl radicals of 4 or more carbon atoms or can favorably have a combined alkyl carbon content of 5 or more carbon atoms.
  • R and R's where R' is hydrogen and R is an alkyl radical of 1-3 carbon atoms are preferred.
  • Poly(N-propionyl)- and poly(N-butyroyl) ethylenimine are most preferred.
  • inertly-substituted By such terms as “inertly-substituted,” “inert substituent” and the like is meant that the substituents are inert to the PAAI's tannin migration inhibition properties.
  • inert substituents include halogen, ethylenic unsaturation, sulfide, nitrile, etc.
  • PAAI's having a weight average molecular weight of at least about 10,000, as determined by gel permeation chromatography, are used in the practice of this invention.
  • the PAAI's here used have an average minimum molecular weight of about 20,000 and preferably of about 40,000.
  • Practical considerations, such as solubility in water, mechanical application, and the like are the only limitations upon the PAAI's average maximum molecular weight although convenience prefers a maximum of about 200,000.
  • PAAI's of this invention are also partially deacylated. PAAI's that are at least about 10 percent deacylated are preferred and those that are at least 15 percent deacylated are most preferred. Again, practical considerations, particularly solubility in water, are the only limitations upon the PAAI's maximum deacylation. About 80 percent, and preferably about 40 percent deacylated PAAI's are generally used.
  • an inhibiting amount of one or more PAAI's is dissolved in an aqueous medium and the resulting solution is applied to a tannin-containing wood substrate in any conventional manner, e.g., brushing, rolling, spraying, dipping, impregnating, etc.
  • the aqueous medium can be water per se or it can be an aqueous solution or dispersion comprising other materials, such as pigments and/or sealers.
  • the concentration of the PAAI in solution and the amount of solution applied can be varied widely, depending upon the wood substrate and the degree of inhibition desired. Satisfactory results are generally obtained at a PAAI concentration of at least about 0.5 weight percent, and preferably of about 1 weight percent. A maximum concentration of about 5 weight percent, and preferably of about 2 weight percent, is generally employed although practical considerations, particularly economics, are the only true maximum limitations.
  • this invention is practiced by adding one or more PAAI compounds, typically in an aqueous solution, to a latex paint prior to applying the paint to the wood substrate.
  • the resulting latex paint contains at least about 0.5 weight percent, and preferably about 1 weight percent, PAAI. Again, only practical considerations limit the maximum PAAI weight percent that can be blended with the latex paint, but generally about 5, and preferably about 2, PAAI weight percent is used.
  • PAAI weight percent is used.
  • Substantially any latex paint that is useful on wood surfaces can be used, the most common types being those based on polymeric esters of acrylic and/or methacrylic acid or on polyvinylacetate.
  • PAAI's of high molecular weight (above 50,000) and high deacylation (above 20 percent) also have desirable thickening properties. As such, these PAAI's can serve to displace some or all of the methylcellulose currently used as a thickening agent in latex paint. PAAI's can thus serve a two-fold function, tannin migration inhibition and thickening, thereby allowing certain economies to be achieved that were heretofore unavailable.
  • tannin-containing wood substrate is intended to include wood, wood composites and wood-derived products containing water-soluble tannins. Any wood substrate capable of receiving an application of an aqueous PAAI can be used in the practice of this invention. Typical examples include: wood, such as redwood, cedar and mahogany; wood composites, such as particle and fiberboard and plywood; and wood-derived products, such as veneer and paper.
  • A. k-65 a commercial white exterior acrylic paint of pH 8.5 manufactured by General Paint and Chemical Co.;
  • D a uniform mixture similar to B but with sufficient ammonium hydroxide to raise the pH to 9.8.
  • a comparison of columns 3 and 4 substantiates the thickening property of PNPEI while a comparison of columns, 3, 4 and 5 illustrates further thickening with time.
  • This thickening property can be advantageous in that PNPEI-containing paints prepared from scratch will require relatively less thickener, e.g., methylcellulose.
  • thickener e.g., methylcellulose.
  • viscosity control is readily had by increasing the pH, as illustrated in column 6.
  • a Hunterlab Reflectometer was used to determine the yellowness (Y) and whiteness (W) of the various samples from the intensity of the blue (B) and green (G) reflectances according to the following formulae:
  • Y is equal to G - B
  • W is equal to 4B - 3G.
  • the reflectometer is described in detail by Hunter in “New Reflectometer and Its Use for Whiteness Measurements", J. Opt. Soc. Am., 50, p. 44 (1960). Since tannin migration varies from board to board, comparative tests were performed on samples of the same board.
  • Redwood boards were used as the tannin-containing wood substrate.
  • a coat of the uniform mixture of B in Example 1 was applied (brushed) to a portion of the board and permitted to dry. Thereafter, a coat of unmodified K-65 was applied (brushed) normal to a portion of the primer coat and it too was permitted to dry.
  • the board was then sequentially aged overnight, exposed to 11/2 hours of rain cycle in a Weather-O-Meter®, and exposed to 1 week of 90 percent relative humidity and 90° F in a tropical humidity chamber. After each exposure Reflectometer readings were taken and these readings are reported in Table II.
  • Example 2 was repeated except that one-half of a redwood board was first primed (brushed) with a 2 percent aqueous PNPEI solution.
  • the yellowness and whiteness values of the various latex coats are reported in Table III.
  • a comparison of the primed and unprimed whiteness values reveals less tannin migration through the latex coats applied to the primed areas.
  • the PNPEI's listed in Table IV were individually blended with portions of K-65 to form uniform mixtures having 1 percent of the respective PNPEI (based on the total weight of paint). These mixtures, i.e., primers, were then brushed on a light and on a dark piece of redwood board at 10 mils and permitted to dry. Subsequently, unmodified K-65 was brushed normal onto the primer coats, allowed to dry and then each primer and topcoat subjected to Hunterlab Reflectometer Measurement. The results are recorded in Tables V and VI.

Abstract

Tannin migration through a latex paint applied to a tannin-containing wood surface is inhibited by applying to the wood surface a linear, partially deacylated poly(N-acyl)alkylenimine, such as poly(N-propionyl)ethylenimine. The poly(N-acyl)alkylenimine can be applied to the wood surface either prior to or concurrently with the latex paint.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to tannin-containing wood substrates. In one aspect, this invention relates to a latex paint applied to the surface of said substrate. In another aspect, this invention relates to a method of inhibiting tannin migration through the latex paint. In yet another aspect, this invention relates to the use of a poly(N-acyl)alkylenimine as a tannin migration inhibitor.
2. Description of the Prior Art
Harren et al., U.S. Pat. No. 3,494,878, teach incorporating an ion exchange resin into an aqueous coating composition comprised of a dispersed emulsion polymer of vinyl addition type and applying the combination to cedar and redwood type substrates. The ion exchange resin is highly cross-linked.
Nordyke et al., U.S. Pat. No. 3,852,087, teach a method of inhibiting the migration of water-soluble tannins through a paint film applied to a tannin-containing wood by incorporating doping agents into certain composite pigments. Enumerated doping agents included the amphoteric compounds of alumina, titania, zirconium, silica or zinc.
Lalk et al., U.S. Pat. No. 3,900,619, teach inhibiting tannin migration through a latex paint applied to the surface of a tannin-containing wood substrate by applying to the substrate a water-soluble S-arylcycloaliphatic sulfonium compound. These sulfonium compounds can be applied to the wood substrate either prior to or concurrently with the application of the latex paint.
Meyer, "Process of Inhibiting Tannin Migration In Tannin-Containing Wood Substrates", Ser. No. 674,789 and filed Apr. 8, 1976, now U.S. Pat. No. 4,075,394 (Feb. 21, 1978), teaches inhibiting tannin migration in tannin-containing wood substrates by applying to the substrate an aqueous solution of a polyalkylenimine, such as polyethylenimine.
SUMMARY OF THE INVENTION
According to this invention, tannin migration through a latex paint applied to a tannin-containing wood surface is inhibited by the novel method comprising applying to the wood surface an inhibiting amount of a linear, partially deacylated poly(N-acyl)alkylenimine (PAAI) having a weight average molecular weight of at least about 10,000. PAAI can be applied to the wood surface either prior to or concurrently with the latex paint. Moreover, high (above 50,000) molecular weight and high (above 20 percent) deacylated PAAI also has desirable thickening properties.
DETAILED DESCRIPTION OF THE INVENTION
PAAI's are known compounds (I) and are readily prepared by the ring-opening polymerization of substituted oxazolines (II) followed by hydrolysis. ##STR1## The substituents are later defined. The ring-opening polymerization is generally conducted in the presence of a cationic polymerization catalyst at a reaction temperature of about 0°-200° C. Typical catalysts include strong mineral acids, organic sulfonic acids and their esters, acidic salts such as ammonium sulfate, Lewis acids such as aluminum trichloride, stannous tetrachloride, borontrifluoride, and organic diazoniumfluoroborates, dialkyl sulfates, and other like catalysts. This ring-opening polymerization is further described by Tomalia et al., J. Polymer Science, 4, 2253 (1966); Bassiri et al., Polymer Letters 5, 871 (1967); and Seeliger, German Pat. No. 1,206,585.
The pre-hydrolyzed polymers thereby obtained are linear N-acylated polyalkylenimines having a molecular structure consisting essentially of repeating units of the formula ##STR2## These polymers are easily deacylated by acid, base or neutral hydrolysis. Hydrolysis (deacylation) is best controlled under acidic conditions and acid hydrolysis is thus preferred. The partially deacylated PAAI's have a molecular structure consisting essentially of repeating units of the formula ##STR3## wherein n (for both III and IV) is the total number of units, h is the number of deacylated units, and n-h is the number of acylated units. R' is typically hydrogen or R, and R is typically an alkyl or an inertly-substituted alkyl radical of 1-3 carbon atoms. The combined carbon content of R and R' generally does not exceed 4 alkyl carbon atoms. R and R' alkyl or inertly substituted alkyl radicals of 4 or more carbon atoms or of a combined alkyl carbon content of 5 or more carbon atoms diminish generally the water solubility of the PAAI polymer, thus diminish generally the polymer's compatibility with latex patent systems, and are thus generally disfavored. However, if R and R' have sufficient hydrophilic, inert substituents, such as ether oxygen, carbonyl, ester, etc., to render the PAAI polymer sufficiently water-soluble to be compatible with a latex paint system, then R and R' can favorably be alkyl radicals of 4 or more carbon atoms or can favorably have a combined alkyl carbon content of 5 or more carbon atoms. For reasons of water solubility and economics, PAAI's where R' is hydrogen and R is an alkyl radical of 1-3 carbon atoms are preferred. Poly(N-propionyl)- and poly(N-butyroyl) ethylenimine are most preferred.
By such terms as "inertly-substituted," "inert substituent" and the like is meant that the substituents are inert to the PAAI's tannin migration inhibition properties. In addition to the hydrophilic substituents mentioned above, other illustrative inert substituents include halogen, ethylenic unsaturation, sulfide, nitrile, etc.
PAAI's having a weight average molecular weight of at least about 10,000, as determined by gel permeation chromatography, are used in the practice of this invention. Typically, the PAAI's here used have an average minimum molecular weight of about 20,000 and preferably of about 40,000. Practical considerations, such as solubility in water, mechanical application, and the like are the only limitations upon the PAAI's average maximum molecular weight although convenience prefers a maximum of about 200,000.
The PAAI's of this invention are also partially deacylated. PAAI's that are at least about 10 percent deacylated are preferred and those that are at least 15 percent deacylated are most preferred. Again, practical considerations, particularly solubility in water, are the only limitations upon the PAAI's maximum deacylation. About 80 percent, and preferably about 40 percent deacylated PAAI's are generally used.
In the practice of this invention, an inhibiting amount of one or more PAAI's is dissolved in an aqueous medium and the resulting solution is applied to a tannin-containing wood substrate in any conventional manner, e.g., brushing, rolling, spraying, dipping, impregnating, etc. The aqueous medium can be water per se or it can be an aqueous solution or dispersion comprising other materials, such as pigments and/or sealers. The concentration of the PAAI in solution and the amount of solution applied can be varied widely, depending upon the wood substrate and the degree of inhibition desired. Satisfactory results are generally obtained at a PAAI concentration of at least about 0.5 weight percent, and preferably of about 1 weight percent. A maximum concentration of about 5 weight percent, and preferably of about 2 weight percent, is generally employed although practical considerations, particularly economics, are the only true maximum limitations.
Preferably this invention is practiced by adding one or more PAAI compounds, typically in an aqueous solution, to a latex paint prior to applying the paint to the wood substrate. The resulting latex paint contains at least about 0.5 weight percent, and preferably about 1 weight percent, PAAI. Again, only practical considerations limit the maximum PAAI weight percent that can be blended with the latex paint, but generally about 5, and preferably about 2, PAAI weight percent is used. Substantially any latex paint that is useful on wood surfaces can be used, the most common types being those based on polymeric esters of acrylic and/or methacrylic acid or on polyvinylacetate.
PAAI's of high molecular weight (above 50,000) and high deacylation (above 20 percent) also have desirable thickening properties. As such, these PAAI's can serve to displace some or all of the methylcellulose currently used as a thickening agent in latex paint. PAAI's can thus serve a two-fold function, tannin migration inhibition and thickening, thereby allowing certain economies to be achieved that were heretofore unavailable.
The term "tannin-containing wood substrate" is intended to include wood, wood composites and wood-derived products containing water-soluble tannins. Any wood substrate capable of receiving an application of an aqueous PAAI can be used in the practice of this invention. Typical examples include: wood, such as redwood, cedar and mahogany; wood composites, such as particle and fiberboard and plywood; and wood-derived products, such as veneer and paper.
The following examples are illustrative of certain specific embodiments of the invention. Unless otherwise noted, all parts and percentages are by weight.
SPECIFIC EMBODIMENTS EXAMPLE 1
Viscosity
The Brookfield viscosities of the following materials were measured:
A. k-65, a commercial white exterior acrylic paint of pH 8.5 manufactured by General Paint and Chemical Co.;
B. a uniform mixture of K-65 (400 g) and poly(N-propionyl)ethylenimine (PNPEI) (28.1 g) having a weight average molecular weight of 320,000 and 59 percent hydrolyzed (deacylated);
C. the uniform mixture of B after aging 24 hours under ambient conditions; and
D. a uniform mixture similar to B but with sufficient ammonium hydroxide to raise the pH to 9.8.
The viscosities were measured with a No. 3 spindle and are reported in Table I.
              TABLE I                                                     
______________________________________                                    
Brookfield RVT Viscosities of K-65                                        
and as Modified with PNPEI                                                
                                    K-65 &                                
                            K-65 &  PNPEI                                 
                  K-65 &    PNPEI   with                                  
        K-65      PNPEI     24 hrs. NH.sub.4 OH                           
RPM.sup.1                                                                 
        (pH=8.5)  (pH=9.2)  Subsequent                                    
                                    (pH=9.8)                              
______________________________________                                    
20.0     3,310    --        --      --                                    
10.0     4,900    --        --       8,670                                
5.0      7,440    15,520    --      12,420                                
2.5     11,920    23,000    38,600  17,840                                
1.0     22,400    41,200    70,400  29,700                                
0.5     40,200    63,800    114,600 46,000                                
______________________________________                                    
 .sup.1 Revolutions per minute.                                           
A comparison of columns 3 and 4 substantiates the thickening property of PNPEI while a comparison of columns, 3, 4 and 5 illustrates further thickening with time. This thickening property can be advantageous in that PNPEI-containing paints prepared from scratch will require relatively less thickener, e.g., methylcellulose. For prepared paints, viscosity control is readily had by increasing the pH, as illustrated in column 6.
EXAMPLE 2
Tannin Migration Inhibition
In this and the following examples, a Hunterlab Reflectometer was used to determine the yellowness (Y) and whiteness (W) of the various samples from the intensity of the blue (B) and green (G) reflectances according to the following formulae:
Y is equal to G - B
W is equal to 4B - 3G.
The greater the W value and/or the lesser the Y value, the more tannin migration has been inhibited and vice versa. The reflectometer is described in detail by Hunter in "New Reflectometer and Its Use for Whiteness Measurements", J. Opt. Soc. Am., 50, p. 44 (1960). Since tannin migration varies from board to board, comparative tests were performed on samples of the same board.
Redwood boards were used as the tannin-containing wood substrate. A coat of the uniform mixture of B in Example 1 was applied (brushed) to a portion of the board and permitted to dry. Thereafter, a coat of unmodified K-65 was applied (brushed) normal to a portion of the primer coat and it too was permitted to dry. The board was then sequentially aged overnight, exposed to 11/2 hours of rain cycle in a Weather-O-Meter®, and exposed to 1 week of 90 percent relative humidity and 90° F in a tropical humidity chamber. After each exposure Reflectometer readings were taken and these readings are reported in Table II.
              TABLE II                                                    
______________________________________                                    
Hunterlab Reflectometer Measurements for PNPEI-                           
Modified K-65 Primer Coat and K-65 Top Coat                               
            Over-                   Tropical                              
            night    Weather-O-Meter®                                 
                                    Chamber                               
Latex System                                                              
            Aging    Rain Cycle-3/2 hr                                    
                                    1 week                                
______________________________________                                    
PNPEI-Modified                                                            
            Y= 8.3     Y=10         Y=14.1                                
K-65 Primer Coat                                                          
            W=40       W=32         W=15.2                                
Unmodified K-65                                                           
            Y= 3.1     Y= 4.3       Y= 5.7                                
Top Coat    W=69.5     W=63.6       W=58.1                                
______________________________________                                    
The above data demonstrates that tannin migration through the primer latex coat is significantly inhibited.
EXAMPLE 3
Tannin Migration Inhibition
Example 2 was repeated except that one-half of a redwood board was first primed (brushed) with a 2 percent aqueous PNPEI solution. The yellowness and whiteness values of the various latex coats are reported in Table III.
              TABLE III                                                   
______________________________________                                    
Hunterlab Reflectometer Measurements for PNPEI-                           
Primed Wood Surface Subsequently Covered With                             
Primer and Top Coats                                                      
           Over-                   Tropical                               
           night    Weater-O-Meter®                                   
                                   Chamber                                
Latex System                                                              
           Aging    Rain Cycle-3/2hr                                      
                                   1-Week                                 
______________________________________                                    
Unmodified Y=3.1    Y=4.0          Y=6.8                                  
K-65 over  W=67.9   W=66.0         W=49.3                                 
Unprimed                                                                  
Surface and                                                               
PNPEI-Mod-                                                                
ified K-65                                                                
Primer Coat                                                               
Unmodified Y=1.9    Y=3.8          Y=7.1                                  
K-65 over  W=74.4   W=65.8         W=51.7                                 
Primed Sur-                                                               
face and                                                                  
PNEPI-Mod-                                                                
ified K-65                                                                
Primer Coat                                                               
PNPEI-     Y=4.8    Y=7.7          Y=10.1                                 
Modified   W=51.1   W=27.5         W=16.8                                 
K-65 Primer                                                               
Coat over                                                                 
Unprimed                                                                  
surface                                                                   
PNPEI-     Y=5      Y=6.9          Y=11.4                                 
Modified   W=52.7   W=35.3         W=18.7                                 
K-65 Primer                                                               
Coat over                                                                 
Primed Sur-                                                               
face                                                                      
______________________________________                                    
A comparison of the primed and unprimed whiteness values reveals less tannin migration through the latex coats applied to the primed areas.
EXAMPLE 4
Molecular Weight Variation
The PNPEI's listed in Table IV were individually blended with portions of K-65 to form uniform mixtures having 1 percent of the respective PNPEI (based on the total weight of paint). These mixtures, i.e., primers, were then brushed on a light and on a dark piece of redwood board at 10 mils and permitted to dry. Subsequently, unmodified K-65 was brushed normal onto the primer coats, allowed to dry and then each primer and topcoat subjected to Hunterlab Reflectometer Measurement. The results are recorded in Tables V and VI.
              TABLE IV                                                    
______________________________________                                    
PNPEI's Blended with                                                      
K-65 to Form                                                              
Example 4 Primer Paints                                                   
            Weight                                                        
            Average                                                       
            Molecular      Hydrolyzed                                     
Reference   Weight         (%)                                            
______________________________________                                    
A            20,000        34                                             
B            50,000        19                                             
C           102,000        19                                             
D           207,000        19                                             
E           320,000        59                                             
______________________________________                                    
              TABLE V                                                     
______________________________________                                    
Hunterlab Reflectometer Measurements                                      
on Light Colored Redwood Board                                            
       Primer Coat   Top Coat                                             
Reference                                                                 
         W         Y         W       Y                                    
______________________________________                                    
A        57.2      6.2       71.6    3.2                                  
B        64.7      4.7       74.4    2.8                                  
C        62.8      4.9       73.4    3.0                                  
D        65.1      4.6       74.5    2.8                                  
E        55.8      6.8       75.7    2.5                                  
K-65*    64        4.8       73.1    3.0                                  
______________________________________                                    
 *Both primer and top coats unmodified                                    
              TABLE VI                                                    
______________________________________                                    
Hunterlab Reflectometer Measurements                                      
on Dark Colored Redwood Board                                             
       Primer Coat   Top Coat                                             
Reference                                                                 
         W         Y         W       Y                                    
______________________________________                                    
A        39.3      7.3       55.9    5.9                                  
B        40.7      6.8       61.7    4.6                                  
C        42.7      6.5       67.9    3.4                                  
D        43.0      6.4       60.8    5.0                                  
E        26.2      10.7      69.4    3.3                                  
K-65*    41.1      4.9       50.6    6.3                                  
______________________________________                                    
 *Both primer and top coats unmodified                                    
The data of Tables V and VI demonstrate that in each case the PNPEI-Modified K-65 latex paint is superior to the unmodified paint as regards tannin migration inhibition through a latex paint coating. Although best results were obtained with a PNPEI additive of 320,000 molecular weight and 59 percent hydrolyzed, acceptable results were obtained with PNPEI-additives at 20,000 molecular weight and 34 percent hydrolyzed and 50,000 molecular weight and 19 percent hydrolyzed.
While the invention has been described with specific reference to particular embodiments, it is to be understood that it is not to be limited thereto but is to be construed bodily and restricted solely by the scope of the appended claims.

Claims (12)

What is claimed is:
1. A method of inhibiting tannin migration through a latex paint applied to a tannin-containing wood surface, the method comprising applying to the wood surface a latex paint blended with an inhibiting amount of a linear, water-soluble, partially deacylated poly(N-acyl)alkylenimine having a weight average molecular weight of at least about 10,000.
2. The method of claim 1 wherein between about 0.5 and about 5 weight percent, inclusive, of the poly(N-acyl)alkylenimine is blended with the latex paint.
3. The method of claim 1 wherein between about 1 and about 2 weight percent, inclusive, of the poly(N-acyl)alkylenimine is blended with the latex paint.
4. The method of claim 2 wherein the poly(N-acyl)alkylenimine has a weight average molecular weight between about 20,000 and about 400,000.
5. The method of claim 3 wherein the poly(N-acyl)alkylenimine has a weight average molecular weight between about 40,000 and about 200,000.
6. The method of claim 4 wherein the poly(N-acyl)alkylenimine is between about 10 percent and about 80 percent deacylated.
7. The method of claim 6 wherein the poly(N-acyl)alkylenimine is between about 15 percent and about 40 percent deacylated.
8. The method of claim 6 wherein the poly(N-acyl)alkylenimine consists essentially of repeating units of the formula ##STR4## wherein R' is hydrogen or R, and R is an alkyl or an inertly substituted alkyl radical of 1-3 carbon atoms and the combined alkyl carbon content of R and R' does not exceed 4 carbon atoms.
9. The method of claim 8 wherein R' is hydrogen.
10. The method of claim 9 wherein R is ethyl or propyl.
11. The method of claim 10 wherein the poly(N-acyl)alkylenimine is poly(N-propionyl)ethylenimine.
12. The method of claim 11 wherein the latex paint is based upon polymeric esters of acrylic and/or methacrylic acid.
US05/754,398 1976-12-27 1976-12-27 Linear, partially deacylated poly(N-acyl)alkylenimines as tannin migration inhibitors Expired - Lifetime US4104228A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
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US4492788A (en) * 1983-01-03 1985-01-08 Allied Corporation Partially deacylated ultra-high molecular weight poly(N-propionylethylenimines)
US4540747A (en) * 1983-06-10 1985-09-10 Sumitomo Chemical Company, Limited Block copolymer
US4547350A (en) * 1983-02-09 1985-10-15 Gesser Hyman D Abatement of indoor pollutants
US4837005A (en) * 1986-09-30 1989-06-06 Union Carbide Corporation Partially hydrolyzed, poly(N-acyl)alkylenimines in personal care
US4873293A (en) * 1986-09-30 1989-10-10 Union Carbide Chemicals And Plastics Company Inc. Partially hydrolyzed, poly(N-acyl alkylenimines) in personal care
US5051283A (en) * 1991-02-12 1991-09-24 Lilly Industrial Coatings, Inc. Process for environmentally sound wood finishing
US5141784A (en) * 1991-02-12 1992-08-25 Lilly Industrial Coatings, Inc Composition of environmentally sound wood finishing
US6075079A (en) * 1995-01-18 2000-06-13 The Dow Chemical Company Fast hardening aqueous coating composition and paint
US20050249884A1 (en) * 2004-05-04 2005-11-10 Neto Nilo M Primer for high extractive-containing wood
WO2011082981A1 (en) 2009-12-17 2011-07-14 Basf Se Aqueous coating formulation
US20110229716A1 (en) * 2009-12-17 2011-09-22 Basf Se Aqueous coating formulation
CN109852126A (en) * 2018-12-29 2019-06-07 烟台大学 A kind of aqueous woodware paint auxiliary agent and preparation method inhibiting tannin diffusion
CN109971239A (en) * 2019-04-10 2019-07-05 烟台大学 It is a kind of inhibit tannin diffusion aqueous woodware paint auxiliary agent and application

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US3450557A (en) * 1966-05-02 1969-06-17 Thilmany Pulp & Paper Co Polyolefin coating composition
US3483145A (en) * 1967-04-17 1969-12-09 Allied Chem Polymers of acyloxyalkyl substituted oxazolines
US3847857A (en) * 1967-11-02 1974-11-12 Rohm & Haas Stain resistant coating composition
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4492788A (en) * 1983-01-03 1985-01-08 Allied Corporation Partially deacylated ultra-high molecular weight poly(N-propionylethylenimines)
US4547350A (en) * 1983-02-09 1985-10-15 Gesser Hyman D Abatement of indoor pollutants
US4540747A (en) * 1983-06-10 1985-09-10 Sumitomo Chemical Company, Limited Block copolymer
US4837005A (en) * 1986-09-30 1989-06-06 Union Carbide Corporation Partially hydrolyzed, poly(N-acyl)alkylenimines in personal care
US4873293A (en) * 1986-09-30 1989-10-10 Union Carbide Chemicals And Plastics Company Inc. Partially hydrolyzed, poly(N-acyl alkylenimines) in personal care
US5051283A (en) * 1991-02-12 1991-09-24 Lilly Industrial Coatings, Inc. Process for environmentally sound wood finishing
US5141784A (en) * 1991-02-12 1992-08-25 Lilly Industrial Coatings, Inc Composition of environmentally sound wood finishing
US6277437B1 (en) 1995-01-18 2001-08-21 The Dow Chemical Company Fast hardening aqueous coating composition and paint
US6075079A (en) * 1995-01-18 2000-06-13 The Dow Chemical Company Fast hardening aqueous coating composition and paint
US6376574B1 (en) 1995-01-18 2002-04-23 The Dow Chemical Company Fast hardening aqueous coating composition and paint
US20050249884A1 (en) * 2004-05-04 2005-11-10 Neto Nilo M Primer for high extractive-containing wood
US7157120B2 (en) 2004-05-04 2007-01-02 Ppg Industries Ohio, Inc. Method for treating wood having a high extractive content
WO2011082981A1 (en) 2009-12-17 2011-07-14 Basf Se Aqueous coating formulation
US20110229716A1 (en) * 2009-12-17 2011-09-22 Basf Se Aqueous coating formulation
US8629207B2 (en) * 2009-12-17 2014-01-14 Basf Se Aqueous coating formulation
CN109852126A (en) * 2018-12-29 2019-06-07 烟台大学 A kind of aqueous woodware paint auxiliary agent and preparation method inhibiting tannin diffusion
CN109852126B (en) * 2018-12-29 2021-11-02 烟台大学 Aqueous wood lacquer auxiliary agent for inhibiting tannin diffusion and preparation method thereof
CN109971239A (en) * 2019-04-10 2019-07-05 烟台大学 It is a kind of inhibit tannin diffusion aqueous woodware paint auxiliary agent and application
CN109971239B (en) * 2019-04-10 2021-10-26 烟台大学 Aqueous wood lacquer auxiliary agent for inhibiting tannin diffusion and application thereof

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